Manufacture of azo dyestuffs derived from z-hydroxynaphthalene-j



Rested July 2, 1929.

, UNITED STATES.

PATENT OFFICE.

HER-MANN WAGNER or noons'r-on-rrm-mam, GERMANY, assrenon, BY MESNE-AS- SIGNMENTS, T GENERAL ANILINE wonxs, Inc, on NEW YORK, N. Y., A CORPORA- TION QF NEW YORK.

MANUFACTURE OF .AZO

DYESTUFFS DERIVED, FROM 2-HYDROXYNAPHTHALENE-3- CARBOXYLIC-ACID-ARYLAMIDES.

No Drawing. Original No. 1,622,690, dated March 29,1927. Serial No. 544,613, filed March 17, 1922. Application for reissue filed February 21, 1929. Serial No. 341,833.

According to U. S. Patent No. 1,034,853 of lVinter et al. granted August 6, 1912, dyestuffs of good properties are obtained by the combination of diam-compounds with arylides of the 2.3-hydroxynaphthoic acid. Now it has been found that dyestuffs of surprisingly favorable properties are obtained by the combination of diazo compounds derived from mononuclear aromatic amines with o-toluidides of 2.3-hydroxynaphthoic acid.

The compounds containing halogen and among these the compounds containing halo-- genin both components are distinguished by their excellent tastness properties.

The new azo dyestuffs are represented by the general formula:

' ,merous cases a better fastness to light. But.

BIT=NR OH wherein B may be a mononuclear aromatic residue, and X may be hydrogen, halogen, or another monovalent substituent. Upon reduction with stannous chloride and hydrochloric acid an aromatic amine and a toluidide of 1-amino-Q-hydroxy-5-naphthoic acid are produced.

An advantage of these dyestuffs as 'compared with the anilido and nitranilido compounds of 2.3-hydroxynaphthoie acid as well as with the compounds cited in great number in the U. S. Patent No. 1,034,853 consists in that they have a. great kier-boiling and a much better discharge ability so that a remarkably good White is obtainable. Moreover, thenew dyestuffs possess a very pure shade. As compared with the compounds of other tolui'dides of 2.3-hydroxynaphthoic acid, those of the o-toluidides show besides other at least equally good properties in nu the special importance of this invention resides in the discovery of a field ofuse tor o-toluidine and o-nitrotoluene respectively. This substance is formed, as it is known, as the chiefproductby nitrating toluene. For the homologues occurring in small quantity especially p-nitrotoluene great domains of utilization are known already, Whereas for the chief substance, the o-nitroto1uene, there has been only a small demand so that it presented a disagreeable waste-product in the chemical industry. Therefore, the discovery of a group of dyestufis, having such excellent fastness properties and at the same time providmg a use for this product, is of very great lmportance.

Manifestly, the fastness properties of the above-described azo dyestufi's derived from' 2 hydroxynaphthalene 3 carboxylic acidarylamides will to some extent be determined by what. mononuclear aromatic residue is selected to occupy the position R, and by what monovalent substituent is selected to occupythe position X, of the above general formula. Since an object of the present invention is to provide dyestuffs ol good fastness properties, it is to be understood that the mononuclear aromatic residue R, and the monovalent substltuent X, of the general formulae hcreinbefore set out and appearmg 1n the appended claims exclude such substituted Examples.

1. The material is padded with a solution of: 20 g. 2.3-hydroxynaphthoic acid-o-toluidid, 60 g. caustic soda solution of 22 B., 20 g. para soap PN, made up to 1 liter.

Then it is dried and printed With the following color: 152 g. 6-nitro-2-to1uidine, 200 cc. water, 24 cc. hydrochloric acid of 22 1%., mix Well to a paste, cool with 150 g'. ice, then ,add 8 g. sodium nitrite dissolved in g.

water, 550 g, tragacant'h (60:1000) and to this are added before using: 20 g. sodium acetate; total, 1 k

The. dyes'tuif has the following structural formula: v

2. The material is padded with a solution of: g. 2.3-hydroxyn'aphthoic acid-o-toluidid, 60 g. caustic soda solution of 22 B., 20 g. para soap PN, made up to 1 liter.

Then it is dried-and printed with the following color: 12.7 g. p-chlor-anilin, 200 g. water, 24 c. c. hydrochloric acid of 22 B.,

' mix Well to a paste, cool with 150 g. ice, then add 8 g. sodium nitrite dissolved in 50 g. vater, 550 g. tragacanth (60 :1000) and, to this are added before using: 20 g. sodium acetate; total, 1 kg.

The dye'stuff has the following structural formula 3. The material is padded with a solution of: 20 g. 2.3-hydroxynaphthoic acidl chloro-toluidid (CH :NI-I: Ol=1:2:4), 65 g. caustic soda solu ion of 22 B., 20 g. sodium ricinolate, made up to 1 liter.

Then it is dried and printed with the following color: 16.8 g. l-nitro-o-anisidin are dissolved with 30 cc. hydrochloric acid. of 22 B. and 200 cc. boiling water, well cooled and then added 150 g. ice. To this is added while stirring 7.2 g. sodium nitrite dissolved in 50 cc. water. The solution is made up with water to 50.0 g.

This diazo solution is mixed with 480 g. tragacanth (60 :1000) and to this are added before using: 20 g. sdium acetate crystallized; total 1 kg.

Thus is obtained a very bright red onthe fibreiofvery good fasteness properties.

v The dyestujfl has the following structural formula OCH: 7

. \G] v i 4. The material is padded with a solution of: 27 g. 2.3-hydroxynaphthoic acid- 4-brom-o-toluidid, 60 g. caustic soda solufore use.

tion of 22 B., 20 g. para soap PN, made up to 1 liter.

Then it is dried and printed with the fol lowing color: 15.7 g. p-chlo-ranisidin,- 200 g, water, 24 cc. hydrochloric acid of 22 B., mix well to a paste, cool with 150 g. ice, then add 8 g. sodiumnitrite dissolved in 50 g.'water, 550 g. tragacanth (60:1000) and to this are added before using:20 g. sodium acetate; total, 1 kg.

The dyestufl has the following structural formula: i

I QCHs ii 01 N Instead of 17.5 g. 4-chlor-3-toluidine the same quantity of 4-chlor-o-toluidine for instance can be used. c

. 6. The yarn is prepared with the following solution: 12.7 g. beta-hydroxynaphthoic aci'd-o-toluidid, 20 cc. caustic soda solution of 34 B., 30 cc. sodium Turkey red oil 50%, 500 cc. hot water, with cold water made up to 1 liter.

The printed yarn is iw'rung and dyed with the following diazo-compound: 17.5 g. 4- chlor-otoluidinehydrochloride are dissolved with 16 cc. hydrochloric acid 22 B. and 200 cc. boiling water, then cooled while adding 150 g.- ice. To this is added a solution of 7.2 g. nitrite in 50 c. c. water while stirring. The solution is made up to 4 liters and to this added 20 g. sodium acetate be,-

- After dyeing, it is well wrung, rinsed and soaped. Thus is obtained a very bright red of excellent fastness properties.

The dyestu-fi' has the following structural formula: g

The dyestuif has the following structural formula CH: 00M

- I claina: Y

1. As new products the water-insoluble azo dyestuffs of the general formula:

wherein R represents a mononuclear aromatic residue, and X represents hydrogen,halogen or another monovalent substituent.

2. As new products the water-insoluble azo dyestuffs of the general formula:

wherein R represents a mononuclear aromatic residue and X represents hydrogen or halogen, one X being halogen and the other X being hydrogen.

3. As new products the water-insoluble azo dyestuffs of the general formula:

I OH OH: R r o ONHOCI wherein R represents a monon'uelear aromatic residue.

acid-o-toluidid' 4. As new products the water-insoluble azo dyestuffs of the general formula:

N: Y l .4 Y CH:

wherein Y represents hydrogen, halogen or alkyl, one Y being halogen, a second Y being alkyl and the other Ys being hydrogen, and

wherein X represents hydrogen or halogen,

one X being halogen and the other Xs being hydrogen. I

5. As new products the water insoluble azo dyestuffs of the general formula:

0 ONH-Q-X wherein Y represents hydrogen, halogen or 9 alkyl, one Y being halogen, a second Y being alkyl and the other Ys being hydrogen, and wherein X represents hydrogen, or halogen, one X being halogen and the other X being hydrogen.

6. As new products the water-insoluble azo dyestuffs of the general formula:

OH OONHOC] wherein Y represents hydrogen, halogen or alkyl, one Y being halogen, a second Y being alkyl and the other Ys being hydrogen. 7 As new products the water-insoluble azo dyestufis of the general formula: 1

OH: Y

o CH /e a -x wherein Y represents hydrogen or halogen,

oneY being halogen, and the other Ys being wherein Y represents hydrogen or halogen, 65 hydrogen, and X represents hydrogen or one Y being halogen, and theother Y being halogen, one X being halogen and the other hydrogen, and wherein X represents hydro- Xs being hydrogen. I gen or halogen, one'X being halogen and the 5 8. As new products the water-insoluble azo other X being hydrogen.

dyestuffs of the general formula: 12. As new products the water-insoluble 70 azo dyestufis of the general formula:

f on a I on I o ONHC C1 80.

wherein Y represents hydrogen or halogen,

one Y being halogen, and the other Y being hydrogen.

13. As new products the water-insoluble H OH: I

, 00NII-OX l V e X, wherein Y represents hydrogen or halogen, one Y being halogen, and the other Ys being hydrogen, and wherein X represents, hydro;

gen or halogen, one X being-halogen and the am dyestuffs of the General formula: 85 other Xs belng hydrogen. I

9.. As new products the water-insoluble azo dyestufl's of the general formula: I O 01 om Y I C I i t C I H: X

i I G ONH- X so I v I x x GONH o1 I wherein X represents hydrogen or halogen,

wherein Y represents hydrogen or Halogen, one X being halogen and the other Xs being I I 1' hydrogen. 2 ,33; gif h n and the other Y Shem-g 14. As new products the water-insoluble 10. As new products the water-insoluble 5Z0 dyestuffs of h general formula 1 19b azo dyestufls of the, general formula: on,

40 I v T onx 1 -01; 3 I m e X CONH -X f 1 p I I I v I r I x X X wherein X represents hydrogen or halogen,

wherein Yvrepresents hydrogen or halogen, 'X b i h lo d th th X b i one Y being halogen, and the other being hydrogen: a .flhydrogen, and whereinX represents hydro- 15 A 116W d t th watepinsoluble f'gen or halogen, one X bemg halogen'and the 3 d t ff f th f m l 'other Xs being. hydrogen 11. As new products the water-insoluble 55 azo dyestuffs of the general formula: f I. I, CH3

oo-' .5 0H CH3 I I I v I In testimony whereof I aflix my signature.

'HERMANN WAGNER. 

